Platinum Group Elements In Rocks Research Articles

Desulphurisation, chromite alteration, and bulk rock PGE redistribution in massive chromitite due to hydrothermal overprint of the Panton Intrusion, east Kimberley, Western Australia

The Central and Western Zones of the Halls Creek Orogen (HCO) of the East Kimberley region of Western Australia host various Paleoproterozoic layered mafic–ultramafic intrusions. The 1856 ± 2 Ma layered mafic–ultramafic Panton Intrusion of the Central Zone contains a reef-type platinum-group element (PGE) mineralisation associated with metamorphosed chromitite horizons. Here we investigate the compositional variation of chromite within the A chromitite layer, or Main Chromitite Layer (MCL), base metal sulphides (BMS), and the associated PGE distribution. Electron-microprobe analysis (EMPA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data reveal complex chemical zoning of the chromite reflecting post-magmatic sub-solidus re-equilibration and fluid–rock interaction during metamorphism of the host rocks. The sulphur isotopic composition of the BMS (δ34S: −1.67 to 2.89‰) suggests negligible contamination of the parental melt by crustal sulphur and thus favours BMS formation due to fractional crystallisation. Furthermore, pentlandite compositions indicate the highest ƒS2 in the centre of the MCL, which coincides with a considerably heavier sulphur isotope composition compared to pentlandite in the surrounding ultramafic host rock. Alteration of the BMS during amphibolite facies hydration of the Panton Intrusion resulted in the formation of secondary bornite and digenite from the chalcopyrite as well as desulphurisation of pyrrhotite and pentlandite to secondary magnetite. The bulk rock PGE concentrations are controlled by the distribution of platinum-group minerals (PGM) due to the low PGE concentrations in BMS. PGM are present as inclusions in chromite, suggesting that they formed under sulphur-undersaturated conditions. Additional PGM are present within the interstitial serpentine-chlorite matrix suggesting that they precipitated during fluid-rock interaction and hydration of the silicate matrix. Likely sources for the remobilised PGE include PGM inclusions in altered rim zones of magmatic chromite and PGE released due to desulphurisation of BMS despite their low PGE concentrations.

Determination of platinum-group elements in rocks by ICP-MS with external calibration after cation exchange separation of matrix elements by KU-2-8 resin

The analytical technique to determine platinum-group elements ( PGEs ) Ru, Rh, Pd, Ir, Pt and Re in the geological samples within 0.1 ng/g – 10 μg/g range and Os on ng/g level in the ultramafic rocks by inductively coupled plasma mass-spectrometry with external calibration and without chemical removal of main interferences of Zr and Hf was proposed. The samples were prepared after their burning by acid decomposition in the open vessels, melting the insoluble residue with NH 4 F and with a subsequent cation exchange separation of PGEs from matrix elements by KU-2-8 resin (Russia). The measurements have been carried out using the high resolution mass-spectrometer Element 2 (Germany). The accuracy of the technique on μg/g level has been verified with reference materials: pyrrhotite ore RP-1 (Russia) and sulfide copper-nickel ore Zh-3 (Russia). In addition, the accuracy of the trace level (ng/g) has been verified by comparison of the results obtained in this study with those reported in the literature for international sample of comparison OPY-1, developed by the International Association of Geoanalysts (IAG). The procedural blanks are 0.000 n ng/ml for Os, 0.00 n ng/ml for Ru, Rh, Re, Ir and 0.0 n ng/ml for Pt and Pd. The detection limits were estimated by taking into account the blanks and their standard deviations (sample mass 1 g, volume 50 ml) and were 0.02 ng/g for Os, 0.07 ng/g for Re, 0.09 ng/g for Rh and Ir, 0.13 ng/g for Ru, 1.0 ng/g for Pt and 1.4 ng/g for Pd respectively. The content of Re was determined in the reference materials RP-1 and Zh-3, and in the sample of comparison OPY-1. Key words : platinum-group elements and Re, inductively coupled plasma mass-spectrometry, chromatographic separation, RP-1, Zh-3, OPY-1, external calibration. (Russian) DOI: http://dx.doi.org/10.15826/analitika.2016.20.3.003 V.I. Men’shikov, V.N. Vlasova, V.I. Lozhkin, Iu.V. Sokol’nikova Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences (IGC SB RAS) Favorsky ul., 1A, Irkutsk, 664033, Russian Federation

A radiogenic Os component in the oceanic lithosphere? Constraints from Hawaiian pyroxenite xenoliths

Platinum Group Element (PGE) concentrations in garnet pyroxenite xenoliths from Oahu, Hawaii, are significantly lower than those in mantle peridotites and show fractionated patterns (e.g. Pd N/Os N = 2–10, Pd N/Ir N = 4–24; N = chondrite normalized) and very high Re N/Os N ratios (∼9–248). Mass balance calculations show that the bulk rock pyroxenite PGE inventory is controlled by the presence of sulfide phases. The 187Os/ 188Os ratios of these pyroxenites vary from subchondritic to suprachondritic (0.123–0.164); and the 187Os/ 188Os ratios show good correlations with bulk rock and clinopyroxene major and trace element compositions, and bulk rock PGE and sulfur abundances. These observations suggest that the Os isotope compositions in these pyroxenites largely reflect primary processes in the oceanic mantle and Pacific lithosphere. In contrast, bulk rock 187Os/ 188Os ratios do not correlate with other lithophile isotopic tracers (e.g. Rb–Sr, Sm–Nd, Lu–Hf) which show limited isotopic variability ( Bizimis et al., 2005). This and the lack of 187Os/ 188Os vs. Re/Os correlations suggest that the range in Os isotope ratios is not likely the result of mixing between long-lived depleted and enriched components or aging of these pyroxenites within the Pacific lithosphere after its formation at a mid-oceanic ridge setting some 80–100 million years ago. We interpret the Os isotopes, PGE and lithophile element systematics as the result of melt–lithosphere interaction at the base of the Pacific lithosphere. The major and trace element systematics of the clinopyroxenes and bulk rock pyroxenites and the relatively constant lithophile element isotope systematics are best explained by fractional crystallization of a rather homogenous parental magma. We suggest that during melt crystallization and percolation within the lithosphere, the parental pyroxenite melt assimilated radiogenic Os from the grain boundaries of the peridotitic lithosphere. This radiogenic Os component may reside in the grain boundary sulfides or other trace phases, and may be due to fluids or melts that had previously percolated through the basal part of the lithosphere during its transit from a mid-oceanic ridge to its present position above the Hawaiian plume. As the solidus of the parental pyroxenite melt is lower than the solidus of the lithospheric peridotite, we envision that the pyroxenite–parent melt selectively assimilated the grain boundary sulfide phases with lower melting temperature as it percolated through the lithosphere, without significantly reacting with the silicate minerals. Thus while the parental melt of these pyroxenites originate within the Hawaiian plume, melt–lithosphere interaction during progressive crystallization may have selectively enriched the resulting melts with radiogenic Os, thereby decoupling Os from the lithophile element isotopes, but retaining a link between Os, PGE and fractional crystallization systematics. In this model, Oahu pyroxenites essentially represent melts from different stages of this melt–mantle reaction process at the base of the lithosphere, and we suggest that this process may also explain the similar Os vs. lithophile element decoupling seen in the rejuvenated volcanism in Oahu and Kauai. We further show that the pyroxenites do not posses the requisite Pt/Re ratios, where upon, recycling and aging would generate the coupled enrichments of 186Os– 187Os isotope ratios observed in Hawaiian and other lavas.

An alternative model for silica enrichment in the Kaapvaal subcontinental lithospheric mantle

The Mg- and Si-rich nature of the sub-cratonic lithospheric mantle (SCLM) beneath the Kaapvaal Craton indicates extensive melt depletion, followed by a Si-enrichment process. Six highly silica enriched peridotites from Kimberley containing high amounts of orthopyroxene (Opx) or garnet (Grt) that are locally concentrated in clots, were investigated to constrain the timing and nature of the Si-enrichment process. A clinopyroxene-bearing lherzolite containing an Opx-clot was studied to quantify the effects of recent metasomatism on the Si-enriched samples. Minerals from the lherzolite, together with Opx from harzburgites and Opx- and Grt-clots have Hf–Nd isotope ratios at the time of kimberlite eruption, 90 Ma, comparable to group I kimberlites and are close to trace element equilibrium with kimberlitic melts. This implies the xenoliths underwent major interaction with kimberlitic melts close to the time of kimberlite eruption. Harzburgites and mineral clots record equilibration pressures and temperatures of, respectively, between 3.5–4.3 GPa and 930–1060 °C. The garnets in Opx-clots have low Lu/Hf and ε Hf(t) −15, whereas garnets from Grt-clots have high Lu/Hf and ε Hf(t) +10. In contrast, Grt from both Grt- and Opx-clots have low Sm/Nd and ε Nd −10. The whole rock platinum group element (PGE) concentrations are an order of magnitude higher in the Grt-clot than the Opx-clot. Measured 187Os/ 188Os range from 0.1085 to 0.1222. The Grt-clot bearing sample yields Nd–Hf–Os isotope model ages that suggest formation in the Neoproterozoic (∼650 Ma). In contrast, an Opx-clot yields T RD ages of 2.8 Ga, which is interpreted as the time of formation of the host harzburgite. The Opx-clots and host harzburgites have comparable Lu–Hf isotope systematics that imply Opx growth at ∼1.3 Ga and hence their formation is not related to the Grt-clots. Garnets from Opx- and Grt-clots have elevated high-field strength element (HFSE) concentrations, and lack HFSE depletion relative to other trace elements with comparable degrees of incompatibility in the mantle (La/Nb < 0.5). In addition, calculated melts in equilibrium with Grt have strongly fractionated REE (Nd/Yb > 300) and HREE depletion (Yb N < 0.1) suggesting equilibration with a hydrous melt that is more HREE depleted than a kimberlitic melt. Previous models that related Si-enrichment to subduction are inconsistent with the lack of HFSE depletion (La/Nb < 0.5). Therefore the favoured model for Opx- and Grt-clot formation is infiltration of a hydrous melt in a within plate geodynamical environment associated with volcanism in the Mid-proterozoic and Neoproterozoic, respectively. This implies that Si-enrichment of the Kaapvaal SCLM may be a consequence of numerous localised magmatic events rather than a single craton-wide process.

Behaviour of Platinum-group elements in the subcontinental mantle of eastern Australia during variable metasomatism and melt depletion

Increasing recognition of complexities in the Platinum-group element (PGE) and Re concentration patterns in mantle samples are challenging the view of chondritic relative abundances in the upper mantle. To investigate the possible causes of PGE abundance variations, a suite of east Australian, mantle-derived, spinel peridotite xenoliths, ranging from fertile lherzolites to depleted harzburgites, and including apatite ± phlogopite ± amphibole bearing samples, have been analysed for their whole rock PGE and Re abundances. Whole rock abundances for 21 samples, combined with mineral separate analyses of 2 xenoliths, are presented to constrain the distribution of the PGEs and Re, their inherent heterogeneity at difference scales, and their behaviour during both melt extraction and metasomatism. Fertile (>2.9 wt% Al 2O 3) xenoliths have broadly chondritic relative PGE abundances, with the significant exception of positive Rh anomalies and variable negative Os anomalies. The high Rh abundances cannot be attributed to melt extraction or metasomatism. Bulk mineral separate PGE-Re analyses of 2 fertile xenoliths indicate less than 6% of the whole rock PGE budget resides in either silicate or oxide (spinel) phases. The remainder of the PGEs, and at least 80% of the whole rock Re budget, are sited in acid-leachable sulfides and less soluble trace phases such as PGE-sulfides or alloys. Individual PGEs partition into different trace phases resulting in small scale heterogeneity of both PGE ratios and concentrations on the order of 8%–20%. Although these trace phases may be present within the mantle, it is more likely at least some exsolved from monosulfide solid solutions at low temperatures. Ir and Rh abundances are consistent with compatible behaviour during melt extraction, whereas Ru, Pt and Pd abundances are consistent with slightly incompatible behaviour and can be modeled by assuming all reside in sulfides within the mantle, with D sulf Ru ∼ D sulf Pt > D sulf Pd. Comparison of PGE abundances between ‘dry’ xenoliths and modally metasomatised xenoliths, suggests the PGEs are not significantly mobilised during interaction with carbonate melts or during metasomatism leading to hydrous mineral growth. Given the problems of various types of secondary alteration processes, including melt extraction and surficial alteration that commonly affect xenoliths, and as within-locality heterogeneity is on a comparable order to any proposed regional heterogeneity, it may be premature to define significant regional differences, or ‘primary’ non-chondritic PGE patterns in lithospheric peridotites.

Dry-chlorination inductively coupled plasma mass spectrometric method for the determination of platinum group elements in rocks

A dry-chlorination procedure has been developed for use in the determination of low concentrations of platinum group elements (PGE) and Au in rock pulps. The PGE and Au, present as native metals, natural alloys and as PGE-(or Au-) bearing sulfide group minerals, are converted by dry-chlorination into PGE (or Au) sodium salts. These salts are dissolved in weak HCl. The solutions are analysed for PGE and Au content by inductively coupled plasma mass spectrometry (ICP-MS). Tests on three reference rock pulps [diluted South African Bureau of Standards Reference Material (SARM)-7 Platinum Ore; diluted INCO S-1800; Nevada Bureau of Mines (NBM) 6a Stillwater] and one gabbro rock showed that the dry-chlorination–ICP-MS method produced results that were usually comparable to, and often better than, fire assay techniques. Reagent contamination was extremely low (Pt⩽1 ng g–1; other PGE and Au⩽0.2 ng g–1). The recoveries of PGE obtained by dry-chlorination–ICP-MS were often >90%.

Abundance and distribution of gold, palladium and iridium in some spinel and garnet lherzolites: implications for the nature and origin of precious metal-rich intergranular components in the upper mantle

The abundance and distribution of Au, Pd, Ir, Cu, Co and Cr has been determined in mantle-derived spinel lherzolite xenoliths in basanites from Mt Porndon (Victoria, Australia) and Kilbourne Hole (New Mexico, U.S.A.) and in garnet lherzolites from the Matsoku and Thaba Putsoa kimberlites (Lesotho). Minerals in the lherzolites concentrate Au, Pd and Ir in the following sequence of increasing platinum group element (PGE) content; garnet, olivine, orthopyroxene, clinopyroxene, spinel. and demonstrate that there exists a real crystallochemical control on the distribution of PGE. Whole rock PGE abundances calculated from the modal mineralogy are less than actually determined and indicate that the bulk of the PGE (60–80%) occur in a sulphide-rich intergranular component. A metasomatic origin for this component is considered to be unlikely and it is proposed that it represents an immiscible sulphide melt which has been retained in the mantle after extraction of a sulphur saturated basic partial melt. This component may in the case of garnet lherzolites have been modified by metasomatic events in the mantle leading to Au depletion and rare earth element addition. Spinel lherzolites are relatively homogeneous at a given locality but differ in their PGE content regionally. The weighted average abundances of PGE in a spinel lherzolite upper mantle are 0.6 ppb. Au, 4.0 ppb Pd. 3.6 ppb Ir. Garnet lherzolites are very heterogeneous and insufficient data is available to allow calculation of geochemically meaningful averages. Spinel lherzolite-basalt based pyrolite contains 0.9 ppb Au, 4.3 ppb Pd, 3.0 ppb Ir, and indicates that the mantle contains an apparent excess of Au over a calculated abundance based upon the siderophilic equilibrium distribution of Au between core and mantle. This excess is considered to be due to failure to consider the chalcophilic nature of Au in the mantle and not to the addition of a meteoritic component to a mantle equilibrated with the core.